EP0011836B1 - Working composition for absorption heat pumps - Google Patents

Working composition for absorption heat pumps Download PDF

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Publication number
EP0011836B1
EP0011836B1 EP79104676A EP79104676A EP0011836B1 EP 0011836 B1 EP0011836 B1 EP 0011836B1 EP 79104676 A EP79104676 A EP 79104676A EP 79104676 A EP79104676 A EP 79104676A EP 0011836 B1 EP0011836 B1 EP 0011836B1
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Prior art keywords
absorber
working
absorption heat
heat pumps
methylamine
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German (de)
French (fr)
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EP0011836A1 (en
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Georg Prof. Dr. Alefeld
Reinhard Radermacher
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems

Definitions

  • the invention relates to a working material pair for operating absorption heat pumps from a working medium and an absorber.
  • absorption heat pumps absorption chillers
  • a suitable absorber For the operation of absorption heat pumps (absorption chillers), a suitable absorber must be found in addition to the working fluid with the desired properties.
  • US-A-1 734278 describes a working fluid system for absorption refrigeration machines, which contains amines and a mixture of water with salts, cf. in particular page 1, lines 32 to 35, 42 to 49, 95 to 97 and page 2, lines 1 and 2 and 20 to 33.
  • the working material pair according to the invention differs from the working material system for absorption refrigeration machines described in US Pat. No. 1,734,278 mainly in that in the system according to the invention the absorber is an aqueous lithium bromide solution.
  • the solvent is an alcohol.
  • the present invention differs as follows:
  • the investigations by Albright et al (ASHRAE Transactions 72, 198 (1966)) and by Unger (Supplement z. Kältetechnik 12, 119 (1957)) on two-substance absorbers also had the aim of changing the absorption properties for the working fluid ammonia, so that the advantages mentioned above could not be achieved.
  • the same corrosion inhibitors can be used as for the LiBr / H Z O system, for example the addition of sodium chromate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Sorption Type Refrigeration Machines (AREA)

Abstract

1. A pair of working substances for operating absorption heat pumps consisting of a working medium and an absorber, characterised in that the working medium is methylamine and the absorber an aqueous lithium bromide solution.

Description

Die Erfindung betrifft ein Arbeitsstoffpaar zum Betrieb von Absorptionswärmepumpen aus einem Arbeitsmittel und einem Absorber.The invention relates to a working material pair for operating absorption heat pumps from a working medium and an absorber.

Für den Betrieb von Absorptionswärmepumpen (Absorptionskältemaschinen) muß zusätzlich zum Arbeitsmittel mit den gewünschten Eigenschaften auch ein geeigneter Absorberstoff gefunden werden.For the operation of absorption heat pumps (absorption chillers), a suitable absorber must be found in addition to the working fluid with the desired properties.

Bisher haben sich die Arbeitsmittel NH3 mit HzO als Absorber bzw. H20 mit einer wäßrigen LiBr-Lösung als Absorber in Kältemaschinen als technisch brauchbar erwiesen.So far, the working materials NH 3 with H z O as an absorber or H 2 0 with an aqueous LiBr solution as an absorber in refrigeration machines have proven to be technically usable.

Zum Zweck der'Reduzierung der Drücke in der Wärmepumpe und aus Sicherheitsgründen wäre es wünschenswert, Ammoniak durch ein anderes Arbeitsfluid, wie z.B. Methylamin, zu ersetzen. Salze, die bei dem Absorptionsvorgang fest bleiben, wie z.B. CaCl2, SrCl2, LiCI, MgClz (L. Vahl, Z. f. d. ges. Kälte-Industrie, 38, 177 (1931)), haben verfahrenstechnische Nachteile, Flüssige Methylamin-Salzlösungen, wie z.B. CH3NH2/NaSCN (US-PS 3 458 448), haben eine zu geringe Ausgasungsbreite. Da man in der Nähe der Löslichkeitsgrenze arbeiten müßte, besteht überdies die Gefahr, daß sich feste Ausscheidungen bilden.For the purpose of 'reducing the pressures in the heat pump and for safety reasons it would be desirable to replace ammonia by another working fluid, such as methylamine. Salts that remain solid during the absorption process, such as, for example, CaCl 2 , SrCl 2 , LiCl, MgCl z (L. Vahl, Z. fd ges. Refrigeration Industry, 38, 177 (1931)), have procedural disadvantages, liquid methylamine Salt solutions, such as CH 3 NH 2 / NaSCN (US Pat. No. 3,458,448), have too little outgassing range. Since one would have to work in the vicinity of the solubility limit, there is also the danger that solid excretions will form.

Die Anwendung von Wasser als Absorber (W. Niebergall, Hdb. d. Kältetechnik Bd. 7 (1959)) scheitert daran, daß die Dampfdruckkurven von Methylamin und Wasser zu nahe beieinander liegen (strichlierte Linien in der Abbildung), so daß sich wiederum ein zu enges Lösungsfeld ergibt.The use of water as an absorber (W. Niebergall, ed. D. Kältetechnik Vol. 7 (1959)) fails because the vapor pressure curves of methylamine and water are too close to each other (dashed lines in the figure), so that again results in a narrow solution field.

Die US-A-1 734278 beschreibt ein Arbeitsstoffsystem für Absorptionskältemaschinen, welches Amine und eine Mischung von Wasser mit Salzen enthält, vgl. insbesondere Seite 1, Zeilen 32 bis 35, 42 bis 49, 95 bis 97 und Seite 2, Zeilen 1 und 2 sowie 20 bis 33.US-A-1 734278 describes a working fluid system for absorption refrigeration machines, which contains amines and a mixture of water with salts, cf. in particular page 1, lines 32 to 35, 42 to 49, 95 to 97 and page 2, lines 1 and 2 and 20 to 33.

Die im CHEMICAL ABSTRACT, Band 79, Nr. 22, 3. Dezember 1973, veröffentlichte Zusammenfassung Nr. 127759r beschreibt ein Arbeitsstoffsystem für Absorptionskältemaschinen, welches Alkohole, Salze und Wasser enthält.Summary No. 127759r, published in CHEMICAL ABSTRACT, Volume 79, No. 22, December 3, 1973, describes a working fluid system for absorption refrigeration machines, which contains alcohols, salts and water.

Demgegenüber ist es Aufgabe der Erfindung, ein spezielles System zun Betrieb von Absorptionswärmepumpen zur Verfügung zu stellen, bei dem keine Ausscheidung der Salzkomponente erfolgt, und mit dem ein optimaler Temperaturbereich er schlossen werden kann.In contrast, it is an object of the invention to provide a special system for operating absorption heat pumps, in which there is no separation of the salt component, and with which an optimal temperature range can be closed.

Diese Aufgabe wird erfindungsgemäß bei einem Arbeitsstoffpaar der oben erwähnten Art dadurch gelöst, daß das Arbeitsmittel Methylamin und der Absorber eine wäßrige Lithiumbromidlösung ist.This object is achieved according to the invention in a working material pair of the type mentioned above in that the working medium is methylamine and the absorber is an aqueous lithium bromide solution.

Das erfindungsgemäße Arbeitsstoffpaar unterscheidet sich von dem in der US-A-1 734 278 beschriebenen Arbeitsstoffsystem für Absorptionskältemaschinen hauptsächlich dadurch, daß bei dem erfindungsgemäßen System der Absorber eine wäßrige Lithiumbromidlösung ist. Demgegenüber ist bei dem aus der US-A-1 734 278 bekannten Arbeitsstoffsystem das Lösungsmittel ein Alkohol. Auch finden sich in dieser Druckschrift keinerlei Hinweise, in einem solchen Arbeitsstoffsystem das spezielle Salz Lithiumbromid zu verwenden.The working material pair according to the invention differs from the working material system for absorption refrigeration machines described in US Pat. No. 1,734,278 mainly in that in the system according to the invention the absorber is an aqueous lithium bromide solution. In contrast, in the working fluid system known from US-A-1 734 278, the solvent is an alcohol. There is also no indication in this document of using the special salt lithium bromide in such a working substance system.

Mit dem erfindungsgemäßen Arbeitsstoffpaar können folgende, nicht-vorhersehbare Vorteile beim Betrieb einer Absorptionswärmepumpe realisiert werden:

  • a) Bei der erfindungsgemäß erfolgenden Verwendung einer Lithiumbromidlösung erfolgt keine Ausscheidung des Salzes, von festen Hydraten oder von festen Amin-Komplexverbundungen im Arbeitsbereich, wie es bei anderen Salzen der Fall ist.
  • b) Erst durch die erfindungsgemäß vorgesehene Kombination H2O/LiBr/CH3NH2 gelingt es, einen optimalen Temperaturbereich zu erschließen und in diesem Temperaturbereich eine optimale Dampfzusetzung mit niedrigem Wassergehalt zu realisieren.
The following, unforeseeable advantages in the operation of an absorption heat pump can be realized with the working material pair according to the invention:
  • a) When using a lithium bromide solution according to the invention, there is no elimination of the salt, of solid hydrates or of solid amine complex compounds in the working area, as is the case with other salts.
  • b) It is only through the combination of H 2 O / LiBr / CH 3 NH 2 provided according to the invention that an optimal temperature range can be developed and optimum steam addition with a low water content can be achieved in this temperature range.

Aufgrund umfangriecher Messungen an verschiedenen Systemen, die in der Abbildung und der Tabelle I exemplarisch dargestellt sind, ergibt sich, daß z.B. durch die Kombination von 3 Gew.Teilen LiBr mit 2 Gew.Teilen Wasser das Lösungsfeld für CH3NHz so weit auseinandergezogen wird, daß diese Kombination LiBr/H2O als Absorber für CH3NHz gut geeignet ist (Abbildung). Diese Kombination bewirkt, daß mit Methylamin als Arbeitsfluid eine Absorptionswärmepumpe mit vergleichbarer Leistungsziffer wie bisher für Arbeitsfluide NH3/H20, jedoch mit einem um einen Faktor 3 niedrigeren Druck, bei gleichen Betriebstemperaturen betrieben werden kann. Außerdem ist die Gefahr der Ausscheidung selbst bei extremer Ausgasung von Methylamin nicht mehr gegeben. Für den Fachmann ist aus Tabelle I, Zeile 2 ersichtlich, daß die Kombination CH3NH2 mit H2O/LiBr als Absorberstoff sogar eine bessere Leistungsziffer erwarten läßt als für die Kombination NH3 mit H20 als Absorber. Außerdem ist die Giftigkeit von Methylamin erheblich geringer als von NH 3.Based on extensive measurements on various systems, which are shown as examples in the figure and Table I, it can be seen that, for example, by combining 3 parts by weight of LiBr with 2 parts by weight of water, the solution field for CH 3 NH z is so far apart that this combination of LiBr / H 2 O is well suited as an absorber for CH 3 NH z (Figure). This combination means that with methylamine as the working fluid, an absorption heat pump with a comparable performance figure as previously for working fluids NH 3 / H 2 0, but with a pressure lower by a factor of 3, can be operated at the same operating temperatures. In addition, there is no longer any risk of excretion even with extreme outgassing of methylamine. For the person skilled in the art, it can be seen from Table I, line 2 that the combination CH 3 NH 2 with H 2 O / LiBr as the absorber substance can even be expected to have a better performance figure than for the combination NH 3 with H 2 0 as the absorber. In addition, the toxicity of methylamine is significantly lower than that of N H 3 .

Ein weiterer Vorteil ergibt sich daraus, daß in der Absorptionsmaschine der Rektifikator in Wegfall kommen kann.Another advantage results from the fact that the rectifier can be eliminated in the absorption machine.

Gegenüber früheren Versuchen, Mehrstoffabsorber zu verwenden, unterscheidet sich die vorliegende erfindung folgendermaßen: Die in der US-A-1 848 918 beschriebene Erfindung bezog sich auf Ammoniak als Arbeitsfluid und hatte zum Ziel, die Neigung der Dampfdruckkurven durch Zusätze zum Absorber so zu verändern, daß sich Schnittpunkte verschiedener Dampfdruckkurven ergeben. Die Untersuchungen von Albright et al (ASHRAE Transactions 72, 198 (1966)) sowie von Unger (Beilage z. Kältetechnik 12, 119 (1957)) über Zweistoffabsorber hatten ebenfalls zum Ziel, die Absorptionseigenschaften für das Arbeitsfluid Ammoniak zu verändern, so daß die obengenannten Vorteile nicht erzielt werden konnten.Compared to previous attempts to use multi-substance absorbers, the present invention differs as follows: The invention described in US Pat. No. 1,848,918 related to ammonia as the working fluid and had the aim of changing the tendency of the vapor pressure curves by adding additives to the absorber in such a way that that there are intersections of different vapor pressure curves. The investigations by Albright et al (ASHRAE Transactions 72, 198 (1966)) and by Unger (Supplement z. Kältetechnik 12, 119 (1957)) on two-substance absorbers also had the aim of changing the absorption properties for the working fluid ammonia, so that the advantages mentioned above could not be achieved.

Zur Verhinderung der Korrosion können die gleichen Korrosionsinhibitoren Verwendung finden wie für das System LiBr/HZO, also z.B. ein Zusatz von Natriumchromat.

Figure imgb0001
To prevent corrosion, the same corrosion inhibitors can be used as for the LiBr / H Z O system, for example the addition of sodium chromate.
Figure imgb0001

Claims (1)

  1. A pair of working substances for operating absorption heat pumps consisting of a working medium and an absorber, characterised in that the working medium is methylamine and the absorber an aqueous lithium bromide solution.
EP79104676A 1978-12-04 1979-11-26 Working composition for absorption heat pumps Expired EP0011836B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79104676T ATE4509T1 (en) 1978-12-04 1979-11-26 PAIR OF WORKING SUBSTANCES FOR OPERATION OF ABSORPTION HEAT PUMPS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782852312 DE2852312A1 (en) 1978-12-04 1978-12-04 SUBSTANCES FOR THE OPERATION OF ABSORBER HEAT PUMPS
DE2852312 1978-12-04

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EP0011836A1 EP0011836A1 (en) 1980-06-11
EP0011836B1 true EP0011836B1 (en) 1983-08-24

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5829259A (en) * 1994-01-13 1998-11-03 Rocky Research Aqueous absorption fluids
US5577388A (en) * 1994-01-13 1996-11-26 Rocky Research Aqueous absorption fluids

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1734278A (en) * 1925-07-07 1929-11-05 Electrolux Servel Refrigerant
DE1519723A1 (en) * 1964-07-24 1970-07-16 Trance Co Absorption mixture for absorption cooling systems
US3458445A (en) * 1967-05-05 1969-07-29 American Gas Ass Absorption refrigeration system containing solutions of monoethylamine with thiocyanates
US3609087A (en) * 1968-02-01 1971-09-28 American Gas Ass Inc The Secondary alcohol additives for lithium bromide-water absorption refrigeration system
SU382667A1 (en) * 1970-06-29 1973-05-25 WORKING BODY VACUUM-ABSORPTION REFRIGERATING

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ATE4509T1 (en) 1983-09-15
EP0011836A1 (en) 1980-06-11
DE2852312A1 (en) 1980-06-12

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